CN105849530A - Spectroscopy apparatus and methods - Google Patents

Spectroscopy apparatus and methods Download PDF

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Publication number
CN105849530A
CN105849530A CN201480065719.1A CN201480065719A CN105849530A CN 105849530 A CN105849530 A CN 105849530A CN 201480065719 A CN201480065719 A CN 201480065719A CN 105849530 A CN105849530 A CN 105849530A
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light
sample
photoelectric detector
bearing
analysis apparatus
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Granted
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CN201480065719.1A
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CN105849530B (en
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托马斯·安东尼·梅森
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Renishaw PLC
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Renishaw PLC
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0208Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using focussing or collimating elements, e.g. lenses or mirrors; performing aberration correction
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0237Adjustable, e.g. focussing
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0248Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using a sighting port, e.g. camera or human eye
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/2803Investigating the spectrum using photoelectric array detector
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/2823Imaging spectrometer
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/2823Imaging spectrometer
    • G01J2003/2826Multispectral imaging, e.g. filter imaging
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/02Mechanical
    • G01N2201/025Mechanical control of operations
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/06Illumination; Optics
    • G01N2201/061Sources
    • G01N2201/06113Coherent sources; lasers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/10Scanning
    • G01N2201/103Scanning by mechanical motion of stage
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/10Scanning
    • G01N2201/11Monitoring and controlling the scan
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/10Scanning
    • G01N2201/11Monitoring and controlling the scan
    • G01N2201/117Indexed, memorised or programmed scan
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/12Circuits of general importance; Signal processing
    • G01N2201/122Kinetic analysis; determining reaction rate

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Spectrometry And Color Measurement (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

This invention concerns spectroscopy apparatus comprising a light source (101) arranged to generate a light profile (110) on a sample, a photodetector (103) having at least one photodetector element (104) for detecting characteristic light generated from interaction of the sample with light from the light source (101), a support (109) for supporting the sample, the support (109) movable relative to the light profile (110), and a processing unit (121). The processing unit (121) is arranged to associate a spectral value recorded by the photodetector element (104) at a particular time with a point on the sample predicted to have generated the characteristic light recorded by the photodetector element (104) at the particular time based on relative motion anticipated to have occurred between the support (109) and the light profile (110).

Description

Spectral analysis apparatus and method
Technical field
The present invention relates to spectral analysis apparatus and method.It is particularly useful in Raman spectrum analysis, but it can be used on an equal basis In the spectrum analysis of other form, such as, fluorescence, narrow linear light photoluminescence or cathodoluminescence are used.
Background technology
Raman spectroscopy equipment is illustrated in No. 5,442,438 United States Patent (USP) (Bei Qide (Batchelder) et al.) Example.The light carrying out self-excitation light source focuses on a bit on sample.Interaction between light and the molecule of sample causes Raman Scattering is for have the frequency shifted relative to excitation laser frequency and the spectrum of wave number.After leaching laser frequency, example As the dispersal devices such as diffraction grating cross over two-dimensional photodetector array (such as, the shape of (CCD) in charge coupled device Formula) disperse this Raman spectrum scattered.Different molecular substances has different characteristic Raman spectrums, and the most described effect Should can be used for analyzing the molecular substance existed.Raman spectrum also can provide out of Memory, such as, the local stress in sample Or strain.
If needing to draw the region of sample rather than only a single point, then known sample is arranged on can orthogonal direction X, On the platform of the upper movement of Y.Or, moveable mirror can cross over the surface deflections light beam of sample in x and y directions.Therefore, The raster scanning to sample can be carried out, thus provide the Raman spectrum at each point in scanning.
At each point in this type of raster scanning, laser beam must be by sufficiently long for the specimen illumination time to allow acquisition to draw Graceful spectrum.Therefore the mapping (map) obtained in the large area of sample can be time-consuming.The most known not with a focus But illuminate sample with line focus.These multiple acquisition spectrum made it possible to simultaneously in line.About CCD light electric-examination Surveying device, its image being arranged to line extends orthogonally with spectral dispersion direction.This makes it possible to be efficiently used light electric-examination Survey the two-dimensional nature of device to obtain multiple spectrum simultaneously.Multiple spectrum is concurrently formed in multiple row or column of ccd array.
US8179526 describes a kind of method, and wherein the electric charge on ccd array is same relative to the movement of line focus with sample Step ground shifts between the element of array.The displacement of electric charge may be on the direction being perpendicular to spectral dispersion direction.Therefore, By succeedingly illuminating multiple point from the light of the diverse location of the length along line focus, though so that it is guaranteed that light intensity edge The length change of line focus, each point is also illuminated by identical total light intensity.
In the embodiment of the method described in US8179526, driving is at the electricity of the movement of the platform of sample installed above Motivation is controlled by platform controller, the shifting of the electric charge between described platform controller and the element controlling ccd array The controller of position is separately.Before the spectrum of the specified target position of record sample, target location is sent to platform courses Device, it activates motor and described platform is driven into target location.The controller controlling ccd array activates ccd array To pass by spectra re-recorded after cycle preset time from target location being sent to platform controller.
This problem arranged is that, for high data collection rate, the position of platform can fall in target location when spectra re-recorded The most a certain distance, thus the inaccuracy in the record position of derivative spectomstry.
Fig. 1 is the chart of the inaccuracy in display location and the change in speed.This chart is in 108ms The data collection rate of 77 row of ccd array.Dotted line and the desired location of dash lines show platform, and dotted line (has length Point) physical location of display platform and its delayed desired location how many.Point 1 is the final time data recorded by CCD, And point 2 and point 3 are reality and the desired location of platform now respectively.From the average speed by having the instruction of puncticulose dotted line Degree is it can be seen that the speed of platform changed in the whole cycle by ccd array record data.
Summary of the invention
According to the first aspect of the invention, it is provided that spectral analysis apparatus, including:
Light source, it is for producing light distribution on sample;
Photoelectric detector, it has at least one photoelectric detector components for detection by sample and the light from light source The characteristic light interacted and produce;
Bearing, it is used for supporting sample, and described bearing can be mobile relative to light distribution;And
Processing unit, it is arranged to based on the relative motion that can occur between bearing and light are distributed through expection, and makes Special time is associated with the point on sample by the spectral value of photoelectric detector components record, the predicted meeting of point on this sample Produce by the characteristic light of photoelectric detector components record at described special time.
In this way, the speed of photoelectric detector record data is not by the communication between photoelectric detector and following controller Speed limit: this controller is used for controlling bearing, and relative to light distribution, (other of such as, point, line focus or light is suitable Pattern) relative movement.Specifically, processing unit can based on about bearing relative to photodistributed relative position Information and make spectral value be associated with the point on sample, this information can be in addition to the time residing for recording light spectrum Time obtains.
Characteristic light can be the light from sample scatter, the light such as produced by Raman scattering.
Photoelectric detector can be activated relative to photodistributed relative motion based on the bearing predicted from previous known location.Example As, bearing can set at the volley, and photoelectric detector is arranged to desired movement based on bearing and thereafter with the time Interval recording light spectrum.
Described equipment can include for driving the bearing motor relative to photodistributed movement.Can control described motor with There is provided bearing relative to photodistributed predetermined motion.
During the measurement cycle, bearing can be at constant speed relative to photodistributed movement, and processing unit is arranged for Control photoelectric detector so that photoelectric detector components during the measurement cycle with time interval recording light spectrum at equal intervals. Bearing and/or light distribution can accelerate to constant speed during the acceleration cycle, and the process cycle is arranged to control photoelectric detector To start the spectral value of recording characteristic light when accelerating end cycle.Recognizable by sampled initial point, and can be from as follows Position sets bearing and/or light distribution at the volley: this position is from running through position clawback, and wherein initial point is distributed by light Illuminate on photoelectric detector components, produce characteristic light so that the acceleration cycle has tied when initial point is in and runs through position Bundle.
Processing unit can be arranged to from known time bearing relative to photodistributed known relative position to calculate that light divides Cloth illuminates described point to produce the time residing for the characteristic light on photoelectric detector components.The spectral value now recorded with After can be relevant to the point on sample.For high data collection rate, perhaps can not determine with the highest speed and transmit Bearing relative to photodistributed relative position with provide light distribution of illumination set point timely information.The present invention can allow photoelectricity Detector can detect and transmit the bearing speed higher data rate recording light relative to photodistributed relative position with ratio Spectrum.
Can calculate that bearing relative to photodistributed relative position from known location relative to photodistributed known motion from bearing. Such as, it will be assumed that bearing is advanced relative to light distribution with constant speed from known location.
Equipment can include the sensor of the position for detecting bearing.Processing unit can be arranged to from detected position Calculate and produce by the point on the sample of the characteristic light of photoelectric detector components record in preset time.Processing unit can be arranged Become the speed determining bearing from detected position, and determine the acceleration of bearing alternatively.Processing unit can be arranged Become based on determined by speed and be optionally based on acceleration and update the time for initiateing photoelectric detector.Such as, Photoelectric detector is being initiateed when the predetermined point on light source lighting sample is to produce characteristic light on photoelectric detector components In the case of, processing unit can be arranged to update the time for initiateing photoelectric detector based on detected position. It is understood, however, that command speed or acceleration criterion (such as, constant speed) can be met in the motion of bearing Time initiate photoelectric detector, and unrelated with the point on the sample now producing characteristic light on photoelectric detector components.
Photoelectric detector components such as (is shifted or reading from photoelectric detector components at spectral value by Accumulating charge during it Before taking) and the sample interval of recording light spectrum can be shorter than and report the position detected of bearing to place in-between The detection time interval of reason unit.Therefore, the point on photoelectric detector components record sample (such as, the continuum of point) The data rate of spectral value can be more than the data rate of the position detected for recording bearing.
Photoelectric detector can include photoelectric detector intervalometer, and photoelectric detector components is arranged to based on from Photoelectric Detection The signal of device intervalometer and recording light spectrum.Can predict that bearing will be in based on the position detected from sensor Photoelectric detector intervalometer is initiateed relative to the time of photodistributed pre-position.Bearing is relative to photodistributed motion May be arranged so that when bearing is in precalculated position, bearing moves with constant speed relative to light distribution.This pre-determined bit Putting can be to run through position.
The electromotor velocity driving the motor of bearing can be controlled based on bearing intervalometer.This bearing intervalometer can be with light Photodetector intervalometer is identical or be different intervalometers.
Processing unit can be arranged to control bearing relative to photodistributed relative movement so that light distribution is opened from following location Beginning scanned samples: in this position by sampled initial point and light layout pitch.In this way, bearing and/or light distribution Required possible constant speed can be accelerated to before light distribution runs through initial point.Bearing and/or light distribution can have default Acceleration rate, and the distance of initial point and light layout pitch can select to be sampled based on predetermined acceleration and user Target velocity determines.Described target velocity can such as be selected according to collection rate by user-selected number directly or indirectly Select.
According to the second aspect of the invention, it is provided that a kind of to sample perform spectrum analysis method, including:
Relative to the mobile sample of light distribution, described smooth distribution of illumination sample is to illuminate the multiple points on sample continuously;
Use the photoelectric detector components detection of photoelectric detector by sample and the interaction of the photodistributed light of formation Characteristic light by described generation;And
Make at special time by photoelectric detector based on the relative motion that can occur between bearing and light are distributed through expection The spectral value of element record produces by the characteristic light of photoelectric detector components record at described special time with predicted meeting Point on sample is associated.
According to the third aspect of the invention we, it is provided that a kind of data medium, it has the instruction being stored thereon, described instruction Processing unit is caused to perform this when being performed by the processing unit of spectral analysis apparatus according to the first aspect of the invention The method of bright second aspect.
According to the fourth aspect of the invention, it is provided that spectral analysis apparatus, comprising:
Light source, it is arranged on sample producing light distribution;
Photoelectric detector, it has at least one photoelectric detector components for detection by sample and the light from light source The characteristic light interacted and produce;
Bearing, it is used for supporting sample, and described bearing can be mobile relative to light distribution;And
Processing unit, it is for controlling the movement of bearing, and wherein said processing unit is arranged to receive to making to use up point The selection in region of the sample of cloth scanning, and make bearing accelerate to predetermined speed from a position so that light distribution run through by During the region being scanned, bearing has reached this predetermined speed.
Processing unit can be arranged to control bearing relative to photodistributed relative movement so that light distribution exists with constant speed Overlying regions scans.
According to the fifth aspect of the invention, it is provided that a kind of to sample perform spectrum analysis method, including:
Receive the selection by the region of scanned sample;
Relative to the light distribution produced on sample by light source, mobile sample is to illuminate continuously in the described region of sample Multiple points;
Use the photoelectric detector components detection of photoelectric detector by sample and the interaction of the photodistributed light of formation Characteristic light by described generation;
Wherein from a position, sample is accelerated to predetermined speed so that sample is when light distribution runs through scanned region Reach described predetermined speed.
According to the sixth aspect of the invention, it is provided that a kind of data medium, it has the instruction being stored thereon, described instruction Processing unit is caused to perform this when being performed by the processing unit of spectral analysis apparatus according to the fourth aspect of the invention The method of the 5th bright aspect.
According to the seventh aspect of the invention, it is provided that spectral analysis apparatus, comprising:
Light source, it is arranged on sample producing light distribution;
Photoelectric detector, it includes that multiple photoelectric detector components is for mutual by sample and the light from light source of detection The characteristic light acted on and produce, described photoelectric detector components is arranged at least one row or column;
Bearing, it is used for supporting sample, and described bearing can be mobile relative to light distribution;And
Processing unit, it is arranged for when bearing moves with predetermined constant speed relative to light distribution initiateing light electric-examination Survey device so that the data of photoelectric detector components recording characteristic light, wherein data are in the Photoelectric Detection of at least one row or column Repeatedly shifting between device element, each continuous displacement occurs after previous displacement equal time distances.
In this way, after the activation, photoelectric detector need not and produce the relative movement between bearing and light distribution Synchronous communication between controller/motor, the restriction to data collection rate is forced in this synchronization.Specifically, can be based in advance If constant speed presets equal time interval.Such as, selecting data displacement constant speed and interval so that about Accumulate at least one from the set point of sample or the characteristic light recorded data in district when data shift along row or column In the continuous photoelectric detector components of individual row or column.
Can (this distance be corresponding to the height of a photoelectric detector components based on the distance on desired time of exposure and sample ) and constant speed is pre-selected.It is also based on photodistributed length (such as, the length of line focus) and perseverance is pre-selected Constant speed degree.
According to the eighth aspect of the invention, it is provided that a kind of to sample perform spectrum analysis method, comprising:
Relative to the light distribution produced on sample by light source, mobile sample is many to illuminate continuously in the region of sample Individual point so that fallen in light electric-examination by the characteristic light of multiple generations by sample and the interaction of the photodistributed light of formation Surveying on multiple photoelectric detector components of device, the plurality of photoelectric detector components is arranged at least one row or column;And
Photoelectric detector is activated so that photoelectric detector components when bearing moves with predetermined constant speed relative to light distribution The data of recording characteristic light, wherein data repeatedly shift between the photoelectric detector components of at least one row or column, often One continuous displacement occurs after previous displacement equal time distances.
According to the ninth aspect of the invention, it is provided that a kind of data medium, it has the instruction being stored thereon, described instruction Processing unit is caused to perform this when being performed by the processing unit of spectral analysis apparatus according to the seventh aspect of the invention The method of bright eighth aspect.
The data medium of the above of the present invention can be the suitable media for providing instruction to machine, such as non-momentary Data medium, such as floppy disk, CD ROM, DVD ROM/RAM (comprise-R/-RW and+R/+RW), HD DVD, Blue light (TM) CD, memorizer (such as, memory stick (TM), SD card, compact flash card or the like), light Disk drive (such as, hard disk drive), tape, any magnetic optical storage device or transient data carrier, such as electric wire Or the signal on optical fiber or wireless signal, such as via wired or wireless network (such as the Internet downloads, FTP transmission or Analog) signal that sends.
Accompanying drawing explanation
The position of the platform of prior art spectrum analysis equipment and the chart of speed when Fig. 1 is to be illustrated in scanned samples;
Fig. 2 is the schematic diagram of Raman spectrum analysis equipment according to an embodiment of the invention;
Fig. 3 shows the line focus and CCD Photoelectric Detection moved relative to sample and produce by Raman spectrum analysis equipment The corresponding displaced of the electric charge in device;And
Fig. 4 is for the position of platform when being illustrated in scanned samples according to the spectral analysis apparatus of the present invention and the figure of speed Table.
Detailed description of the invention
Referring to Fig. 2 and Fig. 3, Raman spectrum analysis equipment 100 includes: light source 101, and it is arranged for producing and uses Light distribution 110 in illumination sample 102;And photoelectric detector 103, it has for detection from sample 102 scattering Multiple photoelectric detector components 104 of light.
Light source 101 includes laser, optical beam expander and for by moulding for laser beam 115 and laser beam is directed to wave filter Suitable lens on 105 and mirror (not shown), these lens and mirror with laser frequency/wave number reflection light but with other frequency/ Wave number transmission light.Laser beam 115 is directed on microscope 106 by wave filter 105.In microscope 106, via one Laser beam 115 is directed across object lens 107 with by laser beam 115 (in this embodiment by individual or multiple suitable mirrors 108 As line focus 110) focus on the sample 102 supported on moveable platform 109.This optical arrangement be similar to The optical arrangement described in US5442438 and WO2008/090350 that the mode quoted is incorporated herein.
Platform 109 is removable to move sample 102 relative to line focus 110 in vertical direction X and Y.There is provided electronic Machine 111a, 111b are for the motion driving platform 109 in each direction.The movement of motor 111a, 111b can Regulate under the control of controller 133 and by intervalometer 113.The position of sensor 114 detection platform 109.Real at this Executing in example, sensor 114 includes the encoder scale chi that is arranged on the relative displaceable element of platform 109 and correspondence Read head.The controller 133 of platform is arranged for communicating with computer 112.
Laser beam 115 illuminates sample 102 and produces scattered light, and the frequency/wave number of this scattered light is with the frequency/wave number of laser not With, such as, Raman diffused light.This scattered light is collected by microscope objective 107 and is directed to photoelectric detector 103.Dissipate Penetrate light and pass wave filter 105 and optical element 116, such as, diffraction grating, for crossing over photoelectric detector 103 light Spectrum ground dispersion scattered light.Through spectrum ground, scattered light is focused on photoelectric detector 103 by condenser lens 117.
In this embodiment, photoelectric detector 103 is the Charged Couple of the two-dimensional array including photoelectric detector components 104 Device (CCD).But, other detector is possible, such as two dimension CMOS photodetector array.Diffraction light Grid cross over the spectrum of the Dispersion on surface scattered light of CCD 103 in directions.For the line focus 110 on sample 102 Each position, cross over photoelectric detector components 104 a scattered scattered light of row 118 be derived from the district on sample 102 Or site (site).
Photoelectric detector 103 includes the processor 140 controlling charge coupled device.Processor 140 is arranged to such as pass through Usb bus communicates with computer 112, and by another order wire (such as, serial communication bus) and platform controller 133 communications.Processor 140 and photodetector array 103 can be configured as single unit.
Camera 119 be mounted so as to can by camera 119 by microscope 106 for laser beam 115 is focused on sample The image of sample 102 captured by identical object lens 107 on 102.The image captured by camera 119 is sent to computer 112 And can show on display 120.
Computer 112 includes the processing unit 121 performing to be stored in the instruction in the computer program in memorizer 122. As existing by described in, computer 112, processor 140 and platform controller 133 control the movement of platform and to CCD 103 In the displacement of electric charge and reading, line focus 110 is carried out raster scanning and record from sample scatter crossing over sample 102 The spectral value of light.It is to be appreciated, however, that in other embodiments, other group of processor and the distribution of process can be used Close.
Initially, sample 102 is placed on moveable platform 109 and uses camera 119 to capture the image of sample by user. This image shows on display 120 and user can use input equipment 123 (such as, keyboard or indicator device) to select By the region 124 of the sample 102 that use line focus 110 scans.System has been collimated so that each pixel pair of image Should known location on platform.Therefore, from the region 124 identified in image, processing unit 121 can determine that use Line focus 110 carrys out the movement of the platform 109 needed for this region of scanned samples 102.
During configuring, user asks about the time of exposure by sampled district.Processing unit 121 is by following operation Calculate the platform 109 desired speed during sampling: the number of the exposed row 118 on CCD 103 is multiplied by platform Distance d of the height corresponding to the single row 118 on CCD 103 at 109, then the time of exposure asked is divided by. This speed can be rounded to the integer part that platform controller 133 accepts.Such as, motor stepping per second integer number 10s。
Between processing unit 121 displacement according to the electric charge between the row 118 of desired speed calculation CCD 103 subsequently Required shift delay (sampling period) so that the motion of platform 109 is Tong Bu with the displacement of electric charge.Such as, may be used Distance d (this distance d is corresponding to the height of the single row 118 on CCD 103) at platform 109 is divided by desired Speed determines required shift delay.
Processing unit 121 passes through processor 140 configuration platform controller 133 to control motor 111a so that platform 109 Accelerate with pre-set constant speed.This configuration can occur before or after the desired speed of above calculating and shift delay.
For platform 109 movement in the Y direction, the leading edge 131 of line focus 110 is initially from the edge in region 124 130 clawback one distances.Determine the distance of line focus 110 clawback so that platform 109 can be in line focus 110 pass-through zone Desired speed is accelerated to before the edge of 124.In order to determine clawback distance, processor 121 determines that platform 109 is necessary The acceleration distance of desired speed when traveling (from static) is accelerated with pre-set constant speed with arrival.Clawback distance is passed through will Calculate in order to provide the additional distance once setting cycle (being 20ms in this embodiment) to be added to acceleration distance, During this is set the cycle, platform 109 should be advanced with constant speed.This additional distance gives a certain leeway and provides one Time cycle, in this time cycle, processing unit 121 can the position of measuring table 109 and determine line focus 110 Leading edge 131 will pass through the time at the edge 130 in region 124, as described in greater detail below.
Original position is may determine that from the known location of clawback distance and region 124.Stop position is wherein line focus 110 Position outside region 124, stop position provides enough distances to leave region 124 at line focus 110 to platform 109 Slow down afterwards.
Processing unit 121 sends order to controller 140, and this order indicates the beginning for platform 109 and stop position And the desired speed of platform 109 and in order to perform the instruction processed as described below.Receiving from computer 112 During to initial order, beginning and stop position and desired speed are sent to platform controller 133 and hold by processor 140 Row is for controlling the order of photoelectric detector 103.
When receiving beginning and stop position, platform controller 133 activates motor 111a, 111b to be driven by platform To original position.
After arriving original position, platform 109 accelerates to desired speed in the Y direction.Platform controller 133 makes Clock pulses for self-timer 113 regulates the speed of motor 111a so that reached desired speed, Motor 111a just maintains setting speed.
During this acceleration cycle, the signal from sensor 114 is sent to processor 140, and processor 140 is remembered Record the position data about the change in the position of platform 109 and time.Processor 140 is burnt from this position data line of prediction When point 110 will pass through the edge 130 in region.This prediction is updated when receiving new data from sensor 114.
Can inquire that during the acceleration cycle platform controller 133 collects position data repeatedly by processor 140.Place Reason device 140 stores the first clock count t from timer internal (not shown)1And by the position of request platform 109 Signal is sent to platform controller 133.In response to receiving this request, platform controller 133 obtains from sensor 114 Reading, and this reading is returned to processor 140.When receiving this reading, processor 140 stores second clock meter Number t2.This read-record is at time (t by processor 1401+t2Occur during)/2.This is based on launching and reception stage flower Take the hypothesis of equal time.
Processor 140 calculates average speed and acceleration from position data within the cycle (reading for such as 3 times) defined in advance Degree.Speed determined by based on and acceleration and update leading edge 131 pass-through zone 124 of line of prediction focus 110 time Between.
Leading edge 131 in line of prediction focus 110 is understood the time at the edge 130 of pass-through zone 124, and processor 140 swashs Live CCD 103 to start the cycle of measuring.This can include Active Timer 126, and this intervalometer regulation electric charge is at CCD 103 The speed of upper displacement.Electric charge on the direction indicated by arrow 127 with correspond to calculated shift delay at equal intervals time Between be spaced and be displaced to adjacent row from every a line.Therefore, cross over along displacement and the line focus 110 of CCD 103 will be by for electric charge The mobile synchronization in the region 124 of sampling.
Fig. 3 shows the part in the region 124 of the sample 102 illuminated by line focus 110.Y illustrates the movement of platform 109 Direction and arrow 127 illustrate the direction that electric charge shifts on ccd array 103.For each district on line focus 110 132 (hereinafter referred to as points), Raman spectrum (by add shadow region instruction) on the direction S be perpendicular to direction Y along The corresponding row 118 of CCD photoelectric detector 103 is disperseed.It is understood that amplified a little 132 big Little, and in fact there is this number point of destination the most again and on CCD 103, there is the row 118 of a lot of this number again.
CCD 103 is exposed to photoconduction and sends a telegraph lotus accumulation in each photoelectric detector components 104.This electric charge represents Raman The spectral value (or frequency range) of spectrum and proportional to the amount of the light received during exposing.Sample 102 is burnt relative to line Point 110 continuously moves so that be incident between the displacement in electric charge on any one photoelectric detector components 104 The scattered light in the district that the point 132 on ratio line focus 110 that light is derived from sample is long.Therefore, photoelectric detector 103 The overlay region of sample 102 will be sampled by adjacent row.
Electric charge shifts on direction 127 between the row of CCD 103, wherein at continuous photoelectricity on the direction of charge displacement Detector element 104 is stably gathered the electric charge about following scattered light: it is given that this scattered light is derived from sample 103 District.The displacement of electric charge is performed until charge displacement in readout register 134.Electricity in readout register 134 Lotus is read out to processor 140.Therefore, between the displacement in electric charge on CCD 103, shift register 134 is held There are the data of a complete spectrum, from sample 102 when this complete spectrum is moved through line focus 110 in given area The illumination of this given area is accumulated.
The spectrum read from CCD 103 is sent to processing unit 121 by processor 140.Processor 140 is using line burnt Point 110 scanning areas 124 whole during continue to position data based on the signal from sensor 114, and These position datas can also be delivered to computer 112.
The processing unit 121 of computer 112 can determine the position of platform 109 at preset time from position data.But, The speed ratio of CCD 103 accumulation data is from the speed of sensor 114 receiving position data faster.Such as, in detector unit In part 104, the sample interval of stored charge is shorter than when the detection being sent to by position measurements between processor 140 Between be spaced.Therefore, the relative fortune that processing unit 121 has occurred based on expection between platform 109 with line focus 110 Move and the complete spectrum read from readout register 134 at special time and prediction can be produced the sample of scattered light District is associated.This known constant speed can advanced from platform 109 and the line focus 110 predicted will run through district The time in territory 124 determines.It is preferable, however, that processing unit 121 also pushes away from the position data received between sweep time Calculate prediction and will produce the district on the sample 102 of Raman spectrum.
Above procedure can be repeated so that the whole region 124 of line focus 110 scanned samples 102 for different X position.
Can produce the district of sample of spectrum based on prediction subsequently and be formed and make recorded spectrum be associated with spatial distribution Mapping.Can be formed about the specific factor of spectrum and map, such as, there is the spy residing for Raman peak values in specific molecular material Standing wave number.
Fig. 4 illustrates the different cycles of the motion of platform 109, it include the acceleration cycle 201, the constant speed cycle 202, Slow down the cycle 203 and wherein platform 109 return to original position to carry out the return week of scanning area about next X position Phase 204.Spectroscopic data is collected so that cross over the electricity of CCD with time interval at equal intervals during the constant speed cycle 202 Displacement in lotus will ensure that district's scattering of the equal length from sample 102 collected by each element 104 of CDD 103 The data of light.
It will be appreciated that in the case of the present invention defined in without departing from claims, can be to embodiments described above Modify and change.Such as, the light distribution of illumination sample can have different shapes, such as focal spot.

Claims (31)

1. a spectral analysis apparatus, including:
Light source, it is for producing light distribution on sample;
Photoelectric detector, it has at least one photoelectric detector components for detection by described sample and from institute The characteristic light stating the interaction of the light of light source and produce;
Bearing, it is used for supporting described sample, and described bearing can be mobile relative to the distribution of described light;And
Processing unit, it is arranged to relative based on can occur between described bearing is distributed with described light through expection Motion, and make to be associated with the point on described sample by the spectral value of described photoelectric detector components record at special time, The predicted meeting of point on this described sample produces by the described spy of described photoelectric detector components record at described special time Property light.
Spectral analysis apparatus the most according to claim 1, wherein, described processing unit arrives based on about described bearing The information of described photodistributed relative position and make spectral value be associated with the point on described sample, described information is being removed The time outside the time residing for described spectral value that records obtains.
Spectral analysis apparatus the most according to claim 1 and 2, wherein, based on according to previous known location prediction Described bearing activate described photoelectric detector to described photodistributed relative motion.
4. according to the spectral analysis apparatus described in any claim in aforementioned claim, wherein, described bearing is being measured Being in constant speed relative to described photodistributed movement during cycle, it is described that described processing unit is arranged for control Photoelectric detector so that described photoelectric detector components during the described measurement cycle with equally spaced time interval record Spectral value.
5. according to the spectral analysis apparatus described in any claim in aforementioned claim, wherein, described bearing and/or Light accelerates to described constant speed during being distributed in the acceleration cycle, the described process cycle is arranged in knot of described acceleration cycle Control described photoelectric detector after bundle and start to record the spectral value of described characteristic light.
Spectral analysis apparatus the most according to claim 5, wherein, is identified sampled initial point, and from such as Lower position set at the volley described bearing and/or light distribution: described position from running through position clawback, wherein said at the beginning of Initial point by described smooth distribution of illumination with on described photoelectric detector components produce characteristic light so that the described acceleration cycle is in institute State when initial point is in described intercepting position and be over.
7. according to the spectral analysis apparatus described in any claim in aforementioned claim, wherein, described processing unit quilt Be arranged to from bearing described in known time relative to special time described in described photodistributed known relative dead reckoning, The characteristic light producing on described photoelectric detector components is put described in light distribution of illumination described at described special time.
Spectral analysis apparatus the most according to claim 7, wherein, from described bearing from described known location relative to Described photodistributed known relative motion calculates to be put described in described smooth distribution of illumination to produce in described photoelectric detector unit The described time residing for characteristic light on part.
Spectral analysis apparatus the most according to claim 8, wherein, described known relative motion be described bearing and/ Or photodistributed default accelerate distribution, and/or described bearing and/or photodistributed pre-set velocity distribution.
10. according to the spectral analysis apparatus described in any claim in aforementioned claim, wherein, described equipment includes using Sensor in the position detecting described bearing.
11. spectral analysis apparatus according to claim 10, wherein, described processing unit is arranged to from detecting Described dead reckoning such time: at this time, the set point on sample described in described smooth distribution of illumination is with described Characteristic light is produced on photoelectric detector components.
12. according to the spectral analysis apparatus described in claim 10 or 11, and wherein, described processing unit is arranged to from inspection The described position measured determines the speed of described bearing, and described speed determined by using determine such described time Between: at this time, the set point on sample described in described smooth distribution of illumination is to produce spy on described photoelectric detector components Property light.
13. spectral analysis apparatus according to claim 12, wherein, described processing unit is arranged to from being determined Described speed determine the acceleration of described bearing, and described acceleration determined by using determine such described time Between: at this time, the set point on sample described in described smooth distribution of illumination is to produce spy on described photoelectric detector components Property light.
14. according to the spectral analysis apparatus described in claim 12 or 13, wherein, described processing unit be arranged to based on Determined by described speed and/or described acceleration update the time for initiateing described photoelectric detector.
15. according to the spectral analysis apparatus described in any claim in claim 10 to 14, wherein, between sample time Every being shorter than detection time interval, during this sample interval, spectral value described in described photoelectric detector components record, Between this detection time interval, the position detected of described bearing is reported to described processing unit.
16. according to the spectral analysis apparatus described in any claim in claim 10 to 15, wherein, and described smooth electric-examination Survey the data rate residing for spectral value of the point on sample described in device element record more than the position for detecting described bearing Described data rate.
17. according to the spectral analysis apparatus described in any claim in aforementioned claim, wherein, described photoelectric detector Including photoelectric detector intervalometer, described photoelectric detector components is arranged in based on from the timing of described photoelectric detector Recording light spectrum at the time of the signal of device.
18. spectral analysis apparatus according to claim 17, wherein, described processing unit is arranged to, in prediction Described bearing to be in relative to activating described photoelectric detector intervalometer at the time of described photodistributed pre-position.
19. according to spectral analysis apparatus described in claim 18, and wherein, described equipment includes for driving described bearing Motor, controls electromotor velocity based on the signal from described photoelectric detector intervalometer.
20. 1 kinds of methods that sample is performed spectrum analysis, including:
Moving described sample relative to light distribution, described in described smooth distribution of illumination, sample is to illuminate described sample continuously On multiple points;
Use the photoelectric detector components detection of photoelectric detector by described sample and the described photodistributed light of formation Interact and by the characteristic light of described generation;And
Based on the relative motion that can occur between described bearing and described light are distributed through expection, make special time by The spectral value of described photoelectric detector components record produces by described photoelectric detector at described special time with predicted meeting Point on the described sample of the described characteristic light of element record is associated.
21. 1 kinds of data mediums, it has the instruction being stored thereon, and described instruction is by according to claim 1 to 19 The processing unit of the spectral analysis apparatus described in middle any claim causes described processing unit to perform according to power when performing Profit requires the method described in 20.
22. 1 kinds of spectral analysis apparatus, including:
Light source, it is arranged on sample producing light distribution;
Photoelectric detector, it has at least one photoelectric detector components for detection by described sample and from institute The characteristic light stating the interaction of the light of light source and produce;
Bearing, it is used for supporting described sample, and described bearing can be mobile relative to the distribution of described light;And
Processing unit, it is for controlling the movement of described bearing, and wherein said processing unit is arranged to receive inciting somebody to action The selection in the region of scanned described sample, and make described bearing accelerate to predetermined speed from a position so that described Light distribution runs through described bearing during scanned described region has been reached described predetermined speed.
23. spectral analysis apparatus according to claim 22, wherein, it is described that described processing unit is arranged to control Bearing is relative to described photodistributed relative movement so that the distribution of described light the most just scans with constant speed.
24. 1 kinds of methods that sample is performed spectrum analysis, including:
Receive the selection by the region of scanned sample;
Relative to the light distribution produced on sample by light source, mobile described sample is to illuminate described sample continuously Multiple points in described region;
Use the photoelectric detector components detection of photoelectric detector by described sample and the described photodistributed light of formation Interact and by the characteristic light of described generation;
Wherein from a position, described sample is accelerated to predetermined speed so that run through scanned in the distribution of described light During described region, described sample has reached described predetermined speed.
25. 1 kinds of data mediums, have the instruction being stored thereon, and described instruction is by according to claim 22 or 23 It is according to claim 24 that the processing unit of described spectral analysis apparatus causes described processing unit to perform when performing Method.
26. 1 kinds of spectral analysis apparatus, including:
Light source, it is arranged on sample producing light distribution;
Photoelectric detector, it includes that multiple photoelectric detector components is for detecting by described sample and from described light The interaction of the light in source and the characteristic light that produces, the plurality of photoelectric detector components is arranged at least one row or column In;
Bearing, it is used for supporting described sample, and described bearing can be mobile relative to the distribution of described light;And
Processing unit, it is arranged for moving with predetermined constant speed relative to the distribution of described light at described bearing Time initiate described photoelectric detector so that the data of characteristic light described in described photoelectric detector components record, wherein data exist Repeatedly shifting between the described photoelectric detector components of at least one row or column described, each continuous displacement occurs away from front After one displacement equal time distances.
27. spectral analysis apparatus according to claim 26, wherein, preset described based on default constant speed Equal time distances.
28. according to the spectral analysis apparatus described in claim 26 or 27, and wherein, described bearing is distributed relative to described light Described predetermined constant speed and described data displacement residing for interval through selection so that for from described sample Set point or the described characteristic light in district and the data that record when described data shift along described row or column described at least The continuous photoelectric detector components of one row or column is accumulated.
29. according to the spectral analysis apparatus described in claim 27 or 28, wherein, based on the time of exposure wanted and correspondence Described constant speed is pre-selected in the distance about described sample of height of a photoelectric detector components.
30. 1 kinds of methods that sample is performed spectrum analysis, including:
Relative to the light distribution produced on described sample by light source, mobile described sample is to illuminate described sample continuously Multiple points in this described region so that by described sample and the interaction of the described photodistributed light of formation by institute State a characteristic light produced and fall on multiple photoelectric detector components of photoelectric detector, the plurality of photoelectric detector components It is arranged at least one row or column;And
Activate described photoelectric detector when described bearing moves with predetermined constant speed relative to the distribution of described light, make Obtaining the data of characteristic light described in described photoelectric detector components record, wherein data are described at least one row or column described Repeatedly shifting between photoelectric detector components, each continuous displacement occurs after previous displacement equal time distances.
31. 1 kinds of data mediums, have the instruction being stored thereon, and described instruction is by according to claim 26 to 29 The processing unit of the spectral analysis apparatus described in middle any claim causes described processing unit to perform according to power when performing Profit requires the method described in 30.
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